Intermediates for preparation of polymeric compositions

ABSTRACT

A Stable Liquid Intermediate comprising of a polyol and/or an acid and/or catalyst and/or water for the preparation of polymeric compositions, the polyol being polyester polyol, a polyoxpropylene- or polyoxypropylene-polyoxyethelene polyol or a mixture thereof. There is disclosed a method of use of said Stable Liquid Intermediate wherein said Stable Liquid Intermediate is mixed with rubber granules.

This invention concerns a method and materials for the production of aStable Liquid Intermediate used in the production of improved porouspolymeric compositions, particularly, though by no means exclusively,suitable for use in the formation of impact absorbing surfaces forsports or children's play areas, safety tiles, compliant substrates forrecreational surfaces and resin bonded stone.

Known such impact absorbing surfaces comprise of particles of natural orsynthetic rubber, such as styrene butatiene-rubber (SBR), andethylene-propylene-diene-monomer-rubber (EPDM) \ for example, adheredtogether by polyurethane based moisture curing pre-polymer (“binder”).The moisture curing pre-polymer is in such quantity as to coat thesurfaces of the particles to cause them to adhere leaving theinterstices between the granules void to enable the uncured pre-polymerto come into contact with airborne water.

The composition may be laid to form a sports or play surface or to forma substrate to another surface such as that provided by synthetic turffor example.

The compositions are prepared on site immediately before installation byaccurately metering out the granules, liquid pre-polymer and, ifnecessary, thoroughly mixing them prior to laying.

A critical characteristic of impact absorbing safety surfaces is thatthey have to deform when subjected to an impacting force. The amount ofdeformation depends on the surface thickness and the compression modulusof the material. However, the safety surfaces must be of such athickness that the elastic compression limit is not exceeded. See FIG. 1

Another critical characteristic of safety surfaces is that they must bestrong enough to withstand every-day wear and tear and the overallstress associated with shrinkage. The strength of polymeric compositionsis proportional to binder concentration—see FIG. 2. However, increasingbinder concentration also increases stiffness which diminishes thecompositions impact attenuation properties. In practical terms thismeans that the polyurethane concentration—for the wearing course atleast—is 15%-20%.

It is the object of the present invention to provide methods andmaterials for the production of a Stable Liquid Intermediate used toproduce porous polymeric composites that mitigates against theaforementioned disadvantages. This is accomplished by modifying themechanics of polymerization to produce inherently stronger and moreimpact absorbing compositions that were hitherto possible.

According to a preferred aspect of the invention there is provided amaterial and method for producing improved porous polymeric compositionscomprising of the following:

Forming a Stable Liquid Intermediate comprising of polyol and/or waterand/or acid and/or catalyst for the preparation of improved polymericcompositions by substantially modifying the mechanics of curing.

The polyol of the Stable Liquid Intermediate may be polyester polyol, apolyoxypropylene- or polyoxypropylene-polyoxyethelene polyol or amixture thereof.

The polyol of the Stable Liquid Intermediate may comprise a polyetherpolyol or a polyester polyol with a molecular weight from 100 to 9.000,preferably from 1.000 to 6.000, more preferably from 1.500 to 5.000 andespecially from 2.000 to 4.000 g/Mol.

The polyol of the Stable Liquid Intermediate may have a functionalityfrom 2 to 5 and preferably from 2 to 3.

The acid of the Stable Liquid Intermediate may be organic or inorganicacid, preferably a P- or S-containing acid and more preferablyphosphoric add; phosphorous acid; sulphuric acid; an ester or mixturesthereof.

Stable Liquid Intermediate may be a reaction product of the polyol andthe acid.

Stable Liquid Intermediate may be produced by reacting the polyol with1.0% to 40.0% by weight preferably 3.0% to 20.0% by weight with the acidcomponent at temperatures between 10.0° C. and 40.0° C. and morepreferably at ambient temperatures.

Stable Liquid Intermediate may be a solution of at least one acid ester;a polyol and water.

Stable Liquid Intermediate may contain catalyst and/or additives such asa pigment.

Stable Liquid Intermediate is mixed with particulate material preferablyat temperatures between 10.0° C. and 50.0° C. and more preferably atambient temperatures to form a Stable Granulate Intermediate.

The invention will be further apparent from the following description,reference being made to Table 7, which concerns, by way of example only,the formation of a Stable Liquid Intermediate and its employment in theprocess of manufacturing an improved polymeric composition used in theinstallation of a recreational surface in accordance with one methodthereof.

A Stable Liquid Intermediate is formed by mixing phosphoric acid andpolyether based polyol—see # 5 of Table 7.

A Stable Granulate Intermediate is formed by mixing Stable LiquidIntermediate (2% by weight) with rubber granules size 1-4 mm (98% byweight)—Table 8#1.

The Stable Granulate Intermediate (88% by weight) is mixed with moisturecuring polyurethane based pre-polymer (12% by weight) to form an uncurednon-coherent mass. In general, the concentration of the binder in theuncured non-coherent mass is 5<20% (by weight).

The uncured non-coherent mass is applied to a stable sub-base andallowed to cure.

Again by way of example, a Stable Liquid Intermediate is formed bymixing phosphoric acid water and polyether based polyol—#4 Table 7.

A Stable Granulate Intermediate is formed by mixing Stable LiquidIntermediate with rubber granules size 1-4 mm—#1 Table 8.

The Stable Granulate Intermediate (95% by weight) is mixed with moisturecuring polyurethane based prepolymer (5% by weight). In general, theconcentration of the binder in the uncured non-coherent mass is 2<10%(by weight).

An appropriate quantity of the mixture is transferred to a tile press.

Heat and pressure is applied to the mixture to cause partial curing.

The tile so formed is de-moulded and allow to fully cure.

Again by way of example, Stable Liquid Intermediate (2%) is mixed withrubber granules (12%) at a manufacturing location to form StableGranulate Intermediate.

Stable Granulate Intermediate is transported to site and mixed with amoisture curing polyurethane based pre-polymer to form an uncurednon-coherent mass.

The uncured non-coherent mass is applied to a stable sub-base andallowed to cure.

In order to explain the uniqueness of the invention experimental resultswill be hereinafter reported.

Test files comprising of Stable Liquid Intermediate (2%) and moisturecuring pre-polymer (12%)—#5 Table 7 were fabricated as herein describedand compared with tiles comprising of the identical moisture curingpre-polymer at 14%; 16% and 18% binder concentration. The tiles wereallowed to cure for seven days. Thereafter the determinations ofUltimate Tensile Strength and % Elongation to Break were performed oneach sample. See FIG. 3.

FIG. 4 shows that tiles comprising of Stable Liquid Intermediate (2%)and moisture curing pre-polymer (12%) had a tensile strength equivalentto a conventional tile comprising of rubber granules bound togetherwith >20% binder. Moreover, the Deformation Coefficient (% Elongation toBreak/UTS) was almost double that of the conventional tile of similartensile strength. See FIG. 5

It will be observed that the % Elongation to Break could not be achievedby a conventional porous polymeric composition. See FIG. 6

This means that porous polymeric safety surfaces and tiles incorporatingthe Stable Liquid Intermediate herein described will deform under impactconsiderably more than conventional porous composites, thus absorbingfar more impact energy yet still be stronger than safety surfacescomprising of conventional polymeric porous compositions.

Moreover, material costs of porous polymeric compositions hereindescribed are considerably less that those associated with conventionalporous polymeric compositions of similar Ultimate Tensile Strength andachieve % Elongation to Break performance that is not achievableemploying conventional porous polymeric technology.

It will be appreciated that it is not intended to limit the invention tothe aforementioned examples only, many variations, such as might readilyoccur to one skilled in the art, being possible, without departing fromthe scope thereof as defined by the appended claims. FIG. 7 defines thepossible permissible combinations of generic components of the StableLiquid Intermediate.

TABLE 7 Preferred range of % (by weight) of the constituents of theStable Liquid Intermediate - with examples Water Acid Catalyst PolyolExample 1 10 < 75% 5 < 15% 0.1 < 5 Make up to 100% 10% Phosporic acid(85%), 50% water 1% Dibutyl tin dilaurate 39% Polyetherpolyol 2 10 < 75%5 < 15% Make up to 48.75% Polyetherpolyol, 100% 50% water, 1.25% Dibutyltin mercaptide 3 10 < 75% Make up to 50% Polyetherpolyol, 100% 50% water4 5 < 15% 0.1 < 5 Make up to 88.85% Polytherpolyol, 100% 10% Phosporicacid (85%), 1.25% Dibutyl tin mercaptide 5 5 < 15% Make up to 90%Polyetherpolyol, 100% 10% Sulfuric acid, 6 10 < 75% 0.1 < 5 48.75%Polyetherpolyol, 1.25% Dibutyl tin mercaptide 50% water

Preferred Species/Description of Constituents:

-   Acid: May be organic or inorganic acid, preferably a P- or    S-containing acid and more preferably phosphoric acid; phosphorous    add; sulphuric acid; an ester or mixtures thereof.-   Polyol: Polyester polyol, a polyoxypropylene- or polyoxypropylene    polyoxyethelene polyol or a mixture thereof.    -   Comprise a polyether polyol or a polyester polyol with a        molecular weight from 100 to 9.000, preferably from 1.000 to        6.000, more preferably from 1.500 to 5.000 and especially from        2.000 to 4.000 g/Mol.-   Catalyst: Tin catalysts, Amines catalysts etc.

TABLE 8 Preferred range of % (by weight) of the constituents of theStable Granulate Intermediate. - with examples. Particulate materialBinder Example 1 Make up to 100% 0.5-5% 2% Stable Liquid Intermediate.98% Rubber Granules. 2 Make up to 100% 0.5-5% 1% Stable LiquidIntermediate. 99% Binder. Rubber Granules: Rubber granules based onbutatiene-rubber (BR), styrene butatiene-rubber (SBR), isoprene-rubber(IR), styrene-isoprenbutatiene-rubber (SIBR),acrylonitrilbutadiene-rubber (NBR), chloroprene-rubber (CR),isobutene-isoprene-rubber (IIR), ethylene-propylene-diene-monomer-rubber(EPDM) and natural rubber (NR), vulcanized thermoplastic (TPV) ormixtures thereof, and preferably a recycling material. Granule RubberGranule size range: 0.1 mm to 100 mm Non-elastomeric Granules:Pea-gravel; stone; recycled glass Non-elastomeric Granules size range:0.1 mm to 10 mm

1. A polymeric composition comprising a stable granulate intermediateand moisture curing polyurethane based prepolymer, said stable granulateintermediate comprising particulate material and a stable liquidintermediate comprising a polyol and/or an acid and/or catalyst and/orwater.
 2. A polymeric composition according to claim 1, wherein saidstable liquid intermediate comprises a polyol, acid, catalyst, andwater.
 3. A polymeric composition according to claim 1, wherein saidstable liquid intermediate comprises a polyol, acid, and water.
 4. Apolymeric composition according to claim 1, wherein said stable liquidintermediate comprises a polyol, catalyst, and water.
 5. A polymericcomposition according to claim 1, wherein said stable liquidintermediate comprises a polyol and water.
 6. A polymeric compositionaccording to claim 1, wherein said stable liquid intermediate comprisesa polyol, acid, and catalyst.
 7. A polymeric composition according toclaim 1, wherein said stable liquid intermediate comprises a polyol andcatalyst.
 8. A polymeric composition according to claim 1, wherein saidstable liquid intermediate comprises a polyol and acid.
 9. A polymericcomposition according to claim 1, wherein said polyol is polyesterpolyol, a polyoxypropylene- or polyoxypropylene-polyoxyethelene polyolor a mixture thereof.
 10. A polymeric composition according to claim 1,wherein said polyol comprises a polyether polyol or a polyester polyolwith a molecular weight from 100 to 9.000, preferably from 1.000 to6.000, more preferably from 1.500 to 5.000 and especially from 2.000 to4.000 g/Mol.
 11. A polymeric composition according to claim 1, whereinthe polyol has a functionality from 2 to 5 and preferably from 2 to 3.12. A polymeric composition according to claim 1, wherein the acid isorganic or inorganic acid, preferably a P- or S-containing acid and morepreferably phosphoric acid, phosphorous acid, sulphuric acid, an esterthereof or mixtures thereof.
 13. A polymeric composition according toclaim 1, wherein said stable liquid intermediate is a reaction productof the polyol and the acid.
 14. A polymeric composition according toclaim 1, wherein said stable liquid intermediate is a reaction productof the polyol with 1.0% to 40% by weight, preferably 3.0% to 20% byweight, with the acid component at temperatures between 10.0° C. and 40°C. and more preferably at ambient temperatures.
 15. A polymericcomposition according to claim 1, wherein there is a solution of atleast one acid ester, a polyol and water.
 16. A polymeric compositionaccording to claim 1, which contains a catalyst and/or additives such asa pigment.
 17. A polymeric composition according to claim 1, whereinsaid stable intermediate liquid is mixed with the particulate materialpreferably at temperatures between 10.0° C. and 50.0° C. and morepreferably at ambient temperatures to form said stable granularintermediate.
 18. A method for the preparation of a moisture curingpolyurethane-based prepolymer, comprising mixing a stable liquidintermediate with rubber granules based on butadiene-rubber (BR),styrene butadiene-rubber (SBR), isoprene-rubber (IR),styrene-isoprenebutadiene-rubber (SIBR), acrylonitrilbutadiene-rubber(NBR), cbloroprenerubber (CR), isobutene-isoprene-rubber (IIR),ethylene-propylene-diene-monomer-rubber (EPDM), and natural rubber (NR),vulcanized thermoplastic (TPV) or mixtures thereof, and preferably arecycling material.
 19. A method according to claim 18, wherein saidstable liquid intermediate comprising a polyol and/or an acid and/orcatalyst and/or water is mixed with non-elastomeric particulate materialsuch as pea-gravel or re-cycled glass granules.
 20. A method accordingto claim 19, wherein the particulate material has a particle size of<0.5 mm to 200 mm.
 21. A method according to claim 18, wherein polymericcompositions are formed by mixing a stable granulate intermediate,comprising a stable liquid intermediate and particulate material, withpolyurethane based binder, and allowing the mixture to set.
 22. A methodaccording to claim 18, wherein the stable granulate intermediate isformed at a central location and shipped to site or formed on-siteimmediately prior to installation.
 23. A method according to claim 21,wherein setting occurs in the presence of water to form a coherent mass.24. A method according to claim 21, wherein the binder is a moisturecuring polyurethane based pre-polymer or an isocyanate with afunctionality>1.5.
 25. A method according to claim 21, wherein thebinder is an aromatic pre-polymer based on MDI, TDI, or a mixturethereof, or an aliphatic pre-polymer, either of which may be based onpolyether or polyester polyol.
 26. A method according to claim 21,wherein the binder concentration is 2% to 30% by weight.
 27. A methodaccording to claim 21, wherein the mixture of stable granulateintermediate and binder is laid on a prepared sub-base and cured to forma coherent mass that can be used as a children's playground, a runningtrack, or a sports hall floor.
 28. A method according to claim 27,wherein the compliant coherent mass can be used as an under layer,interface layer, or a base layer for artificial turf or floors, or is amoulded article, or in combination with mineralic components is astone-blended polymeric mortar floor.